JP2008213200A - Gas barrier laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a gas barrier laminate such as a gas barrier film or the like excellent in gas barrier functionality of oxygen, carbon dioxide, steam, etc., especially gas barrier functionalty under a high-humidity condition. <P>SOLUTION: The gas barrier laminate includes at least two layers (Y) containing a polymer (a) of a multivalent metal salt of a unsaturated carboxylic compound on a base material layer. Further, at least one of a plurality of the layers (Y) containing the polymer (a) is composed of the polymer (a) of the multivalent metal salt of the unsaturated carboxylic compound and a vinyl alcohol polymer (b). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a gas barrier laminate such as a gas barrier film having transparency and excellent gas barrier properties such as oxygen and water vapor, and particularly excellent gas barrier properties under high humidity.

In recent years, as a barrier material against oxygen or water vapor, inorganic oxides such as silicon oxide and aluminum oxide have been formed on film substrates by vacuum deposition, sputtering, ion plating, chemical vapor deposition, etc. A transparent gas barrier film is attracting attention.
And since this transparent gas barrier film is a film obtained by depositing an inorganic oxide on a base material surface made of a biaxially stretched polyester film that is generally excellent in transparency and rigidity, the deposited layer can be used for friction during use. When used as a packaging film, the inorganic oxide may be cracked by rubbing or stretching during post-processing printing or laminating or filling the contents, and the gas barrier property may be lowered.
On the other hand, a method of laminating a polyvinyl alcohol having a gas barrier property and an ethylene / vinyl alcohol copolymer on a biaxially stretched film substrate (for example, Patent Document 1), or a composition of polyvinyl alcohol and poly (meth) acrylic acid A method of coating a biaxially stretched film substrate (for example, Patent Document 2) has been proposed. However, the gas barrier film formed by laminating polyvinyl alcohol has a reduced oxygen barrier property under high humidity, and the composition of polyvinyl alcohol and poly (meth) acrylic acid is sufficiently esterified to form a film. In order to improve the gas barrier property, heating at a high temperature for a long time is required, which causes a problem in productivity, and the gas barrier property under high humidity is insufficient. Further, since the film is colored by reacting at high temperature for a long time and the appearance is impaired, improvement for food packaging is necessary.
On the other hand, since a composition of polyvinyl alcohol and poly (meth) acrylic acid requires a long reaction at a high temperature for esterification, a method of adding a crosslinking agent component such as an isocyanate compound to polyacrylic acid (for example, a patent) Document 3) and a method of reacting with a metal ion (for example, Patent Document 4) have been proposed. In this method, polyacrylic acid is crosslinked with a crosslinking agent component as described in Examples. As shown, it requires treatment at 180 to 200 ° C. for 5 minutes and at a high temperature.
Further, the substrate layer (X) has an absorbance A ₀ based on νC═O of a carboxylic acid group near 1700 cm ⁻¹ and an absorbance A based on νC═O of a carboxylate ion near 1520 cm ⁻¹ in an infrared absorption spectrum. A gas barrier film comprising a layer (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt having a ratio (A ₀ / A) of less than 0.25 is known. Improvement is required (Patent Document 5).

JP-A-60-157830 (Claims) Japanese Patent No. 3203287 (Claim 1) JP 2001-310425 A (Claim 1, Example 1) JP 2003-171419 A (Claim 1, Table 1) WO2005 / 108440 (Claim 1)

  Therefore, an object of the present invention is to obtain a gas barrier laminate such as a gas barrier film having transparency and excellent gas barrier properties such as oxygen, carbon dioxide gas, and water vapor, particularly gas barrier properties under high humidity.

The present invention has a gas barrier property such as a gas barrier film characterized in that the base layer (X) has at least two layers (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt. It relates to a laminate. Furthermore, in the present invention, at least one of the plurality of layers (Y) containing the polymer (a) is an unsaturated carboxylic acid compound polyvalent metal salt polymer (a) and a vinyl alcohol heavy polymer. The present invention relates to a gas barrier laminate such as a gas barrier film characterized by comprising the combination (b).
In the present invention, an inorganic vapor deposition layer (Z) is further provided in the middle of the gas barrier layer in which the base layer (X) and the layer (Y) containing the polymer (a) are laminated or outside the layer (Y). The present invention relates to a gas barrier laminate such as a gas barrier film described above, which is a laminated gas barrier layer.

Further, in the present invention, two of the plurality of layers (Y) containing the polymer (a) are laminated adjacent to each other, and the proportion of the vinyl alcohol polymer (b) in one layer is the other. The present invention relates to a gas barrier laminate such as a gas barrier film characterized in that it is lower (including a substantially free aspect) than the proportion of the vinyl alcohol polymer in the layer.
The present invention also relates to a gas barrier laminate such as a gas barrier film in which a protective layer (U) is further laminated on the surface of the gas barrier laminate such as the gas barrier film.

  According to the present invention, by using two or more gas barrier layers comprising a layer (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt as a gas barrier laminate such as a gas barrier film, Not only is a laminate such as a film having particularly excellent gas barrier properties under high humidity obtained, but these layers are formed from an unsaturated carboxylic acid compound polyvalent metal salt polymer (a) and a vinyl alcohol polymer (b). ) -Containing layer (Y) can provide a gas barrier laminate such as a gas barrier film excellent in not only gas barrier properties but also impact resistance.

Gas barrier laminates such as gas barrier films A gas barrier laminate such as a gas barrier film used in the present invention is a layer containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt in a base layer (X) ( The present invention relates to a gas barrier laminate such as a gas barrier film having at least two layers Y).
Among the gas barrier laminates of the present invention, the thickness of the gas barrier film can be variously determined according to the application, but usually the thickness of the base material layer (X) is 5 to 500 μm, preferably 5 to 100 μm. Preferably, the thickness of the layer (Y) containing the copolymer (a) of unsaturated carboxylic acid compound polymetal salt is 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.00. When the inorganic vapor deposition layer (Z) is used, the thickness is 0.001 to 10 μm, preferably 0.005 to 5 μm, and the total thickness of the gas barrier film is 20 to 750 μm, more preferably Is in the range of 25-430 μm.

Base material layer (X)
Among the gas barrier laminates of the present invention, the gas barrier film can be used without any particular limitation as a base material layer (X) constituting it, such as a film, sheet or tape made of a thermoplastic resin.
As the thermoplastic resin, various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or these And the like. Of these, polypropylene, polyester, polyamide and the like are preferable thermoplastic resins having good stretchability and transparency, and polyesters such as polyethylene terephthalate and polyethylene naphthalate are particularly preferable because of excellent barrier properties and heat resistance.
One preferred embodiment of the present invention is a gas barrier film in which the base material layer (X) is a layer containing inorganic fine particles.

Substrate layer containing inorganic fine particles (X-1)
As the base material layer (X-1) containing inorganic fine particles, a layer composed of a propylene-based polymer in which inorganic fine particles are usually blended in an amount of 0.5 to 10% by weight is suitable. As propylene-based polymers, in addition to propylene homopolymers, binary or ternary with propylene as a main component and olefins such as ethylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene. Random copolymers, block copolymers, and the like can be used. The inorganic fine particles can be used without particular limitation as long as the average particle diameter is about 0.1 to 10 μm. Examples include calcium carbonate, titanium dioxide, barium sulfate, magnesium sulfate, silica, mica, synthetic mica, alum, and zeolite. These may have a surface coated with various polymers as required.
As the shape of these inorganic fine particles, those having various aspect ratios such as a spherical shape, a plate shape, a scale shape, and a needle shape can be used.

These base material layers (X) can be any of non-stretched and at least uniaxially stretched, and the stretched base material layer is excellent in heat resistance, rigidity, transparency and gas barrier properties. In addition, in order to improve the adhesion with the layer (Y), the surface of these base material layers (X) is treated with, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coat treatment, and flame treatment. A surface activation treatment such as the above may be performed.
Layer (Y) containing polymer (a)
As the layer (Y) provided on at least two or more layers on one side or both sides of the base material layer (X), a layer (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt is suitable. .

Polymer (a) of unsaturated carboxylic acid compound polyvalent metal salt
The polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt can be obtained by polymerizing an unsaturated carboxylic acid polyvalent metal salt.
The unsaturated carboxylic acid compound forming the unsaturated carboxylic acid compound polyvalent metal salt used in the unsaturated carboxylic acid compound polymer (a) is α, β-, such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid. It is a carboxylic acid compound having an ethylenically unsaturated group, and has a polymerization degree of less than 20, preferably a monomer or a polymer having a polymerization degree of 10 or less. When a polymer (polymer compound) having a degree of polymerization exceeding 20 is used, a salt with a polyvalent metal compound described later may not be completely formed. As a result, it is obtained by polymerizing the metal salt. The layer may have poor gas barrier properties under high humidity. These unsaturated carboxylic acid compounds may be one kind or a mixture of two or more kinds.
Among these unsaturated carboxylic acid compounds, it is easy to form a salt in which the monomer is completely neutralized with a polyvalent metal compound, and a polymer layer obtained by polymerizing the salt is laminated on at least one side of the base material layer. A gas barrier laminate such as a gas barrier film is preferable because it is particularly excellent in gas barrier properties under high humidity.

Polyvalent metal compound The polyvalent metal compound which is a component forming the unsaturated carboxylic acid compound polyvalent metal salt according to the present invention is a metal or metal compound belonging to groups 2A to 7A, 1B to 3B and 8 of the periodic table. Specifically, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc ( Zn), bivalent or higher metals such as aluminum (Al), oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfates or sulfites of these metals Such as salt. Among these metal compounds, divalent metal compounds are preferable, and magnesium oxide, calcium oxide, barium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and the like are particularly preferable. When these divalent metal compounds are used, the gas barrier property under high humidity of the film obtained by polymerizing the salt with the unsaturated carboxylic acid compound is particularly excellent. At least one kind of these polyvalent metal compounds is used, and only one kind may be used or two or more kinds may be used in combination. Among these polyvalent metal compounds, Mg, Ca, Zn, Ba and Al, and particularly Zn are preferable.

Unsaturated carboxylic acid compound polyvalent metal salt The unsaturated carboxylic acid compound polyvalent metal salt, which is a component constituting the polymer (a) of the unsaturated carboxylic acid compound polyvalent metal salt used in the present invention, has the above-mentioned degree of polymerization. It is a salt of an unsaturated carboxylic acid compound of less than 20 and the polyvalent metal compound. These unsaturated carboxylic acid compound polyvalent metal salts may be one kind or a mixture of two or more kinds. Among such unsaturated carboxylic acid compound polyvalent metal salts, the polymer layer from which zinc (meth) acrylate is obtained is particularly excellent in the hot water resistance, which is preferable.

  The layer (Y) containing the polymer (a) in the present invention is within the range not impairing the object of the present invention, and polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethyleneimine Water-soluble polymers such as starch, gum arabic and methylcellulose, acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, polyesters, polyurethanes and other high molecular weight compounds Various additives such as lubricants, slip agents, anti-blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers may be included, and wetting with the substrate described below Various surfactants and the like may be included in order to improve the properties and adhesion. The proportions of these other components can be varied as required.

Among these, since the vinyl alcohol polymer (b) is easy to coat the base material layer (X) and has excellent gas barrier properties, it is desirable to use it together.
That is, the layer (Y) containing the polymer (a) of the present invention is preferably composed of a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt and a vinyl alcohol polymer (b). .

Vinyl alcohol polymer (b)
Examples of such a vinyl alcohol polymer include polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, and a modified vinyl alcohol polymer. Polyvinyl alcohol has no particular problem as long as it can be mixed, but preferably has a degree of polymerization of 100 to 3000, more preferably 200 to 2500, and most preferably 300 to 2000. Within this range, the base layer is easily coated with an aqueous solution and has good stretchability and gas barrier properties. The degree of saponification is 90% or more, preferably 95% or more. Within this range, the gas barrier property is good. Moreover, you may use olefin containing polyvinyl alcohol from water resistance or extending | stretching property. The olefin content is 0 to 25 mol%, preferably 1 to 20 mol%, more preferably 2 to 16 mol%, and the olefin is preferably those having 4 or less carbon atoms, such as ethylene, propylene, n-butene, isobutene and the like. Among them, ethylene is most preferable from the viewpoint of water resistance.
A suitable example of the vinyl alcohol polymer is a modified vinyl alcohol polymer.

Modified vinyl alcohol polymer (b1)
As the modified vinyl alcohol polymer (b1), a reactive group is added to the vinyl alcohol polymer (b) by adding, substituting, or esterifying various known reactive groups (reactive groups). Examples thereof include those modified by bonding and those obtained by copolymerization of a vinyl ester such as vinyl acetate and an unsaturated compound having a reactive group. Examples of these reactive polymerizable groups include (meth) acrylate groups, (meth) acryloyl groups, (meth) acrylamide groups, vinyl groups, allyl groups, styryl groups, thiol groups, silyl groups, acetoacetyl groups, and epoxy groups. It is done. The amount of the reactive group can be appropriately determined, but since the gas barrier property inherent to the vinyl alcohol polymer may be impaired when the amount of the OH group of the vinyl alcohol polymer serving as the substrate is decreased, usually, The amount of reactive groups is in the range of 0.001 to 50 mol% (the total of reactive groups and OH groups is 100 mol%).
As a method for producing the modified vinyl alcohol polymer (b1), various reactive groups (reactive groups) having various known reactivities are added to the vinyl alcohol polymer (b), and reactive groups are bonded by esterification or the like. And a saponified copolymer obtained by copolymerizing a vinyl ester such as vinyl acetate and an unsaturated compound having a reactive group. There is no particular limitation as long as it has a sex group.
As the modified vinyl alcohol polymer (b1), those having a polymerization degree of 100 to 3000, preferably 300 to 2000 can be used. From the viewpoint of gas barrier properties of the polymer obtained in combination with the unsaturated carboxylic acid compound polyvalent metal salt (a), those having a high saponification degree of 70 to 99.9% are preferably used, particularly 85 to 99.99. 9% is preferred.
Specific examples of reactive groups possessed by these modified vinyl alcohol polymers (b1) include, for example, (meth) acrylate groups, (meth) acryloyl groups, (meth) acrylamide groups, vinyl groups, allyl groups, and styryl. Group, thiol group, silyl group, acetoacetyl group, epoxy group and the like. The amount of reactive groups in the modified vinyl alcohol polymer can be determined as appropriate, but if the amount of OH groups in the vinyl alcohol polymer serving as the substrate decreases, the gas barrier properties inherent to the vinyl alcohol polymer are impaired. Since there is a possibility, normally, the quantity of a reactive group exists in the range of 0.001-50 mol% (the sum total of a reactive group and OH group is 100 mol%). The modified vinyl alcohol polymer (b1) is preferably soluble in water, lower alcohols, organic solvents and the like, and particularly preferably soluble in water or water-lower alcohol mixed solvents.
By using the modified vinyl alcohol polymer (b1) modified with these reactive groups as one of the components, the modified vinyl alcohol is mixed with the unsaturated carboxylic acid compound polyvalent metal salt (a) for polymerization. A layer (Y) having improved gas barrier properties under low humidity is obtained, which is made of a polymer in which at least a part of the polymer (b1) and the unsaturated carboxylic acid compound polyvalent metal salt (a) has some bonds.
Specific examples of such a modified vinyl alcohol polymer (b1) include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. with a part of the OH group of the vinyl alcohol polymer serving as a substrate. A (meth) acrylate group-modified vinyl alcohol polymer (b1) obtained by reacting with a carboxylic acid compound having an α, β-ethylenically unsaturated group or a derivative thereof to introduce a (meth) acrylate group; isothiuronium salt or thiol A vinyl monomer having acid ester and vinyl acetate are copolymerized, and the resulting polymer is decomposed with an acid or base to form a thiol group. A method of introducing a group, polymerizing vinyl esters in the presence of thiolic acid, and saponifying the resulting polymer at the end of the molecule A thiol group-modified vinyl alcohol polymer (b1) having a thiol group (—SH group) in a part of the OH group of the vinyl alcohol polymer as a substrate, which is obtained by a method of introducing only a thiol group; A method of adding a silyl group by post-modification using a silylating agent such as organohalogen silane, organoacetoxy silane, organoalkoxy silane to a vinyl alcohol polymer or a vinyl acetate polymer containing a carboxyl group or a hydroxyl group, or acetic acid Saponification of copolymers of vinyl and silyl group-containing olefinically unsaturated compounds such as vinyl silane and (meth) acrylamide-alkyl silane, and silanol which is an alkoxysilyl group, an acyloxysilyl group or a hydrolyzate thereof in the molecule Obtained by a method of introducing a silyl group such as a group or a salt thereof. A silyl group-modified vinyl alcohol polymer having a trialkoxysilane group such as a trimethoxylane group or a triethoxysilane group, a tricarbonyloxysilane group, etc. as part of the OH group of the vinyl alcohol polymer used as a substrate. (B1 c): A method in which a vinyl alcohol polymer is dispersed in an acetic acid solvent and diketene is added thereto, and the vinyl alcohol polymer is previously dissolved in a solvent such as dimethylformamide or dioxane. An acetoacetyl group having an acetoacetyl group in a part of the OH group of the vinyl alcohol polymer used as a substrate, which is obtained by a method of adding diketene to a vinyl alcohol polymer or a method of directly contacting a diketene gas or liquid diketene with a vinyl alcohol polymer. Acetyl group-modified vinyl alcohol polymer (b1 d); A monomer having a reactive functional group is copolymerized with vinyl acetate and then saponified to introduce a reactive functional group into the side chain, or a method of introducing a reactive functional group into the side chain of polyvinyl alcohol by a polymer reaction , (Meth) acrylamide group, allyl group, vinyl group, styryl group, intramolecular double bond, in the molecule by various known methods such as a method of introducing a reactive functional group to the terminal using chain transfer reaction, Examples thereof include a modified vinyl alcohol polymer formed by adding other radical polymerization groups such as a vinyl ether group, and a modified vinyl alcohol polymer formed by adding a cationic polymerization group such as an epoxy group or a glycidyl ether group.
Among these modified vinyl alcohol polymers (b1), the layer made of the polymer obtained by using the (meth) acrylate group-modified vinyl alcohol polymer (b1 b) is a gas barrier under high humidity and low humidity. Excellent in oxygen properties (oxygen barrier properties), without deterioration in gas barrier properties (hot water resistance) after hydrothermal treatment, and flexible, and in such a laminate in which such a layer is formed, especially films as packaging materials When used in the above, the heat seal strength is improved.

(Meth) acrylate group-modified vinyl alcohol polymer (b1)
As the (meth) acrylate group-modified vinyl alcohol polymer (b1), the amount of (meth) acryloyl groups (compared with —OH group; esterification rate) is preferably 0.001 to 50%, more preferably Is in the range of 0.1 to 40%. When the esterification rate is less than 0.001%, the hot water resistance and flexibility of the resulting layer (Y) may not be improved, while when the esterification rate exceeds 50%, the hot water resistance of the obtained layer (Y) may be improved. There is a possibility that the oxygen barrier property and the like are not improved.
The (meth) acrylate group-modified vinyl alcohol polymer (b1a) according to the present invention includes, for example, a vinyl alcohol copolymer and (meth) acrylic acid or (meth) acrylic acid halide, (meth) acrylic anhydride. And (meth) acrylic acid derivatives such as (meth) acrylic acid esters in the presence or absence of a catalyst such as Bronsted acid, Bronsted base, Lewis acid, Lewis base, metal compound, etc. Is obtained. Further, (meth) acrylic having a functional group in the molecule that reacts with OH group of vinyl alcohol copolymer and vinyl alcohol copolymer such as glycidyl (meth) acrylate and 2-isocyanatoethyl (meth) acrylate, for example. The (meth) acrylate group can also be indirectly introduced into the vinyl alcohol copolymer by reacting with an acid derivative.

Thiol group-modified vinyl alcohol polymer (b1)
As the thiol group-modified vinyl alcohol polymer (b1b), a vinyl monomer having an isothiuronium salt or a thiol acid ester and vinyl acetate are copolymerized, and the resulting polymer is decomposed with an acid or a base to form a thiol group. Thiol acetic acid, thiol propionic acid, thiol butyric acid and other thiols, including organic thiol acid having a -COSH group, a method of introducing a reactive functional group into the side chain of a polyvinyl alcohol polymer by polymer reaction In the presence of carboxylic acid, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate, vinyl laurate, vinyl stearate are polymerized, and the resulting polymer is saponified to end the molecule. A thiol group is added to the molecule by a known method such as a method of introducing a thiol group only into In polymer, typically, a thiol group modification ratio is in the range of 0.1 to 50 mol%.
As these thiol group-modified vinyl alcohol polymers (b1b), for example, “M-115” and “M-205” are manufactured and sold by Kuraray Co., Ltd. under the trade name of Kuraray M polymer.

Silyl group-modified vinyl alcohol polymer (b1)
Examples of the silyl group-modified vinyl alcohol polymer (b1) include a vinyl alcohol polymer or a vinyl acetate polymer containing a carboxyl group or a hydroxyl group, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, and vinyltrichloro. Silylation by post-modification using silylating agents such as organohalogen silanes such as silane and diphenyldichlorosilane, organoacetoxy silanes such as trimethylacetoxysilane and dimethyldiacetoxysilane, or organoalkoxysilanes such as trimethoxysilane and dimethyldimethoxysilane Group addition method, or vinyl acetate and, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris- (β-methoxyethoxy) silane, vinyltriacetoxysilane Allyltrimethoxysilane, allyltriacetoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxysilane, vinyltriiso Vinyloxysilanes such as propoxysilane, vinyltributoxysilane, vinyltrihexyloxysilane, vinylmethoxydihexyloxysilane, vinyldimethoxyoctyloxysilane, or 3- (meth) acrylamide-propyltrimethoxysilane, 3- (meth) acrylamide- Propyltriethoxysilane, 3- (meth) acrylamide-propyltri (β-methoxyethoxy) silane, 2- (meth) acrylamide 2-methylpropyltrimethoxysilane, 2- (meth) acrylamide-2-methylethyltrimethoxysilane, N- (2- (meth) acrylamide-ethyl) -aminopropyltrimethoxysilane, 3- (meth) acrylamide-propyl Triacetoxysilane, 2- (meth) acrylamide-ethyltrimethoxysilane, 1- (meth) acrylamide-methyltrimethoxysilane, 3- (meth) acrylamide-propylmethyldimethoxysilane, 3- (meth) acrylamide-propyldimethylmethoxy Silane, 3- (N-methyl- (meth) acrylamide) -propyltrimethoxysilane, 3-((meth) acrylamide-methoxy) -3-hydroxypropyltrimethoxysilane, 3-((meth) acrylamide-methoxy) In the molecule obtained by a method of saponifying a copolymer with a silyl group-containing olefinically unsaturated compound such as (meth) acrylamide-alkylsilane such as propyltrimethoxysilane, an alkoxysilyl group, an acyloxysilyl group or these The polymer etc. which have silyl groups, such as a silanol group or its salt which is a hydrolyzate, can be mentioned. The modification amount of the silyl group is usually in the range of 0.1 to 50 mol%.
As these silyl group-modified vinyl alcohol polymers (b1 c), for example, “R-1130”, “R-2105” and “R-2130” are manufactured and manufactured by Kuraray Co., Ltd. under the trade name of Kuraray R polymer. Sold.

Acetoacetyl group-modified vinyl alcohol polymer (b1 d)
The acetoacetyl group-modified vinyl alcohol polymer (b1 d) is obtained by adding and reacting a liquid or gaseous diketene to the solution, dispersion or powder of the vinyl alcohol polymer, The degree of acetoacetylation is in the range of 1 to 10 mol%, preferably 3 to 5 mol%.
As these acetoacetyl group-modified vinyl alcohol polymers (b1 d), for example, trade names of “Gosefimer Z100”, “Z200”, “Z200H” and “Z210” from Nippon Synthetic Chemical Industry Co., Ltd. Manufactured and sold in
These modified vinyl alcohol polymers are preferably soluble in water, lower alcohols, and organic solvents, and those that are particularly soluble in water-lower alcohol mixed solvents are preferred.

In the aqueous solution of vinyl alcohol polymer including these modified vinyl alcohol polymers, solvents other than water, for example, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, or other diethyl ether, tetrahydrofuran, etc. Can be added alone or in combination of two or more as required. In addition, a wettability improver, an antistatic agent, and other various additives can be added to the polyvinyl alcohol polymer as long as the characteristics of the present invention are not impaired.
When these vinyl alcohol polymers (b) are used in combination, the layer (Y) containing the polymer (a) of the present invention generally has a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt of 1 (1). It is usually composed of ˜99% by weight and the vinyl alcohol polymer (b) from 1 to 99% by weight.
Among them, polymer (a) of unsaturated carboxylic acid compound polyvalent metal salt 60 to 98% by weight, vinyl alcohol polymer (b) 2 to 40% by weight, particularly (a) 70 to 95% by weight, (b) 5 to 30% by weight (the sum of (a) and (b) is 100% by weight) is preferable.

Method for producing gas barrier film (1)
Among the gas barrier laminates of the present invention, as a method for producing a gas barrier film, the unstretched or stretched base material layer (X) contains an unsaturated carboxylic acid compound polyvalent metal salt having a polymerization degree of less than 20 A method of polymerizing an unsaturated carboxylic acid compound polyvalent metal salt after coating the solution (s) to form a layer (Y) containing a polymer (a) of the unsaturated carboxylic acid compound polyvalent metal salt There is.

  As a method for preparing a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20, the unsaturated carboxylic acid compound and the polyvalent metal compound are reacted in advance and unsaturated. The polyvalent metal salt of the carboxylic acid compound may be used as a solution, or the unsaturated carboxylic acid compound and the polyvalent metal compound may be directly dissolved in a solvent to form a polyvalent metal salt solution.

  As a method for producing the gas barrier film of the present invention, when the unsaturated carboxylic acid compound and the polyvalent metal compound are directly dissolved in a solvent, that is, a solution containing the unsaturated carboxylic acid compound and the polyvalent metal compound is used. In this case, it is preferable to add the polyvalent metal compound in an amount exceeding 0.3 chemical equivalent ratio with respect to the unsaturated carboxylic acid compound. When a mixed solution having a polyvalent metal compound addition amount of 0.3 chemical equivalent ratio or less is used, a polymer layer having a large content of free carboxylic acid groups is obtained, and as a result, a stretched film having a low gas barrier property is obtained. There is a fear. In addition, the upper limit of the amount of polyvalent metal compound added is not particularly limited, but when the amount of polyvalent metal compound added exceeds 1 chemical equivalent ratio, unreacted polyvalent metal compound increases. The ratio is preferably less than the ratio, preferably less than the 2 chemical equivalent ratio.

In addition, the chemical equivalent ratio in this invention shows the chemical equivalent ratio of the polyvalent metal compound with respect to an unsaturated carboxylic acid compound, and is a value calculated by the following formula | equation.
Chemical equivalent ratio = (number of moles of polyvalent metal compound) × (valence of polyvalent metal compound) / number of moles of carboxyl group contained in unsaturated carboxylic acid compound For example, calcium hydroxide (molecular weight 74 g) as the polyvalent metal compound The chemical equivalent ratio is 1 when 37 g of acrylic acid monomer (molecular weight 72 g / mol) is mixed as an unsaturated carboxylic acid compound.

In addition, when a mixed solution of an unsaturated carboxylic acid compound and a polyvalent metal compound is used, the unsaturated carboxylic acid compound is usually added while the unsaturated carboxylic acid compound and the polyvalent metal compound are dissolved in a solvent. Although a valent metal salt is formed, it is preferable to mix for 1 minute or more in order to ensure the formation of the polyvalent metal salt.
Examples of the solvent used for the solution of the unsaturated carboxylic acid compound polyvalent metal salt include water, lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, organic solvents such as acetone and methyl ethyl ketone, and mixed solvents thereof. Most preferred.

As a method of applying the solution (s) of the unsaturated carboxylic acid compound polyvalent metal salt to the surface of the base material layer (X), various known methods, for example, a method of applying the solution to the surface of the base material layer, A method of immersing the base material layer in the solution, a method of spraying the solution on the surface of the base material layer, a method of applying with a brush or the like can be employed.
Examples of the method for applying the solution (s) containing a polyvalent metal salt of an unsaturated carboxylic acid compound to the film-like base material layer (X) include an air knife coater, a direct gravure coater, a gravure offset, and an arc gravure coater. , Gravure reverse and jet nozzle type gravure coaters, top feed reverse coaters, bottom feed reverse coaters and reverse feed roll coaters such as nozzle feed reverse coaters, 5-roll coaters, lip coaters, bar coaters, bar reverse coaters, die coaters, etc. Using various known coating machines, the amount of the unsaturated carboxylic acid compound polyvalent metal salt in the solution (s) (solid content) is 0.05 to 10 g / m ² , preferably 0.1 to 5 g / m. ^What is necessary is just to apply | coat so that it may become ² .

  When the unsaturated carboxylic acid compound polyvalent metal salt is dissolved, other unsaturated carboxylic acids (di) such as methyl (meth) acrylate and ethyl (meth) acrylate, as long as the object of the present invention is not impaired. Monomers such as ester compounds, vinyl ester compounds such as vinyl acetate, or low molecular weight compounds, lubricants, slip agents, anti-blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers, etc. In order to improve the wettability with the base material layer, various surfactants and the like may be added.

In order to polymerize the solution (coating layer) of the unsaturated carboxylic acid compound polyvalent metal salt formed (coated) on the base material layer (X), various known methods, specifically, for example, ionizing radiation Examples of the method include irradiation and heating.
When using ionizing radiation, it is not particularly limited as long as the wavelength region is an energy ray in the range of 0.0001 to 800 nm. Examples of such energy rays include α rays, β rays, γ rays, X rays, visible rays, Ultraviolet rays, electron beams, etc. are raised. Among these ionizing radiations, visible light in the wavelength range of 400 to 800 nm, ultraviolet light in the range of 50 to 400 nm, and electron beam in the range of 0.01 to 0.002 nm are easy to handle and the devices are widespread. Therefore, it is preferable.

  When using visible light and ultraviolet light as ionizing radiation, it is necessary to add a photopolymerization initiator to the solution of the unsaturated carboxylic acid compound polyvalent metal salt. As the photopolymerization initiator, known ones can be used. For example, 2-hydroxy-2methyl-1-phenyl-propan-1-one (trade name; Darocur 1173, manufactured by Ciba Specialty Chemicals), 1-hydroxy-cyclohexyl-phenyl ketone (Ciba Specialty Chemicals, trade name; Irgacure 184), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals, trade name) Irgacure 819), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals) ), Α-hydroxyketone, acylphosphine Mixture of oxide, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (trade name; Essaure KT046 manufactured by Lamberti Chemical Specialty), Esacure KT55 (Lamberti Chemical Specialty), 2,4,6- A radical polymerization initiator manufactured and sold under the trade name of trimethylbenzoyldiphenylphosphine oxide (trade name; Speed Cure TPO manufactured by Ramson Fire Chemical Co., Ltd.) can be mentioned.

  Furthermore, a polymerization accelerator can be added to improve the polymerization degree or polymerization rate, and examples thereof include N, N-dimethylamino-ethyl- (meth) acrylate and N- (meth) acryloyl-morpholine. .

When the main polymerization is performed by irradiating with ionizing radiation, the ionizing radiation dose is usually in the range of 1 to 1000 mJ / cm ² , preferably 5 to 300 mJ / cm ² , particularly 10 to 200 mJ / cm ^2. preferable. By setting the irradiation amount in such a range, a gas barrier laminate such as a gas barrier film having a polymerization rate of 80% or more, preferably 90% or more can be stably obtained.

Among the gas barrier laminates of the present invention, the gas barrier film comprises a base layer (X) as (X) and a layer (Y) containing the polymer (a) as (Y ¹ ), (Y ² ), (Y ³ ), (Y ⁴ )
(X) / (Y ¹ ) / (Y ² )
(X) / (Y ¹ ) / (Y ² ) / (Y ³ )
(X) / (Y ¹ ) / (Y ² ) / (Y ³ ) / (Y ⁴ )
An example of a laminated structure expressed as “etc.” can be given.
^{Incidentally, (Y 1), (Y} 2), (Y 3), the content of the polymer (a) included in each of ^{(Y 4)} may be the same or may be different from one another. Further, the contents of the polymer (b) contained in each layer may be the same or different.

The gas barrier laminate such as the gas barrier film of the present invention has a layer (Y) between the base layer (X) and the layer (Y) containing the polymer (a) or the polymer (a). An inorganic vapor-deposited layer (Z) is also provided on the outside.
These gas barrier laminates such as gas barrier films can be produced by forming the first layer (Y) on the base material layer (X) and further forming the second layer (Y). it can.
When two or more layers (Y) are provided, the structure of each layer (Y) may be the same, for example, the polymer (a) of unsaturated carboxylic acid compound polyvalent metal salt and vinyl alcohol. It is also possible to change the composition ratio and type of the polymer (b).
For example, the ratio of the vinyl alcohol polymer (b) in the plurality of layers (Y) is sequentially decreased, and the layer (Y) in contact with the inorganic vapor deposition layer (Z) described later is substantially replaced with the vinyl alcohol polymer (b). The aspect made into the layer which does not contain can also be illustrated.

Inorganic vapor deposition layer (Z)
As the inorganic vapor-deposited layer (Z), any conventionally known vapor-deposited layer such as a film can be used without any particular limitation. Especially, it is desirable that it is a vapor deposition film whose surface is smooth. For example, it is a film containing elements such as aluminum, zinc, indium, silicon and tin and, if necessary, these metals and oxygen. In these, oxygen can increase the transparency of the film. Such an inorganic vapor deposition film can be formed using a dry film forming method such as a CVD method, a PVD method, a sputtering method, a plasma CVD method, or a CAT-CVD method. The thickness of the inorganic vapor-deposited film (thickness per layer) can be appropriately selected within the range of 0.1 to 1000 nm, particularly 5 to 500 nm, more preferably 30 to 200 nm. When the thickness of the inorganic vapor deposition film is thin, the gas barrier film has insufficient oxygen gas barrier properties, and when it is thick, the vapor deposition layer easily cracks.

The aspect of the barrier film on which the inorganic vapor deposition layer (Z) is laminated is that the base layer (X) is (X), and the layer (Y) containing the polymer (a) is (Y ¹ ), (Y ² ). , (Y ³ ) and the inorganic vapor deposition layer (Z) as (Z),
(X) / (Y ¹ ) / (Z) / (Y ² )
(X) / (Z) / (Y ¹ ) / (Y ² )
(X) / (Y ¹ ) / (Y ² ) / (Z)
(X) / (Z) / (Y ¹ ) / (Y ² ) / (Y ³ )
An example of a laminated structure expressed as “etc.” can be given.
^{Incidentally, (Y 1), (Y} 2), the content of the polymer (a) included in each of ^{(Y 3)} may be the same or may be different from one another. Further, the contents of the polymer (b) contained in each layer may be the same or different.
In these gas barrier films, an inorganic vapor deposition layer (Z) is provided in advance on the base material layer (X), and then the first layer (Y) is formed, and the second layer (Y) is further formed. Can be manufactured. Or it can manufacture by forming the 1st layer (Y) in the base material layer (X), providing an inorganic vapor deposition layer (Z) after that, and forming the 2nd layer (Y) further. it can.

In another aspect of the present invention, two of the plurality of layers (Y) containing the polymer (a) are laminated adjacent to each other. In this case, the proportion of the vinyl alcohol polymer (b) in one layer is lower than the proportion of the vinyl alcohol polymer in the other layer, and the embodiment does not substantially contain, and the proportion of the vinyl alcohol polymer. It is desirable to make the layer (Y) in the case where it is low or substantially not contained adjacent to the inorganic vapor deposition layer (Z).
When the layer (Y) containing these vinyl alcohol polymers (b) is used in combination, the structure of one layer (Y) is that the polymer (a) of the unsaturated carboxylic acid compound polyvalent metal salt is 1 to 99. The vinyl alcohol polymer (b) is usually composed of 1 to 99% by weight, of which (a) is 60 to 98% by weight, (b) is 2 to 40% by weight, It is preferable that a) is 70 to 95% by weight and (b) is 5 to 30% by weight (the sum of (a) and (b) is 100% by weight).
For example, the concentration ratio of the vinyl alcohol polymer (b) in each of the one layer (Y) and the other layer (Y ′) is the same as the concentration ratio of one layer (Y). It is desirable that the layer (Y ′) is composed of a layer that is 1/2 or less of the concentration ratio, particularly 1/3 or less, particularly preferably a layer that is not substantially included.

Protective layer It is desirable to provide a protective layer (U) capable of protecting the layer (Y) in the outermost layer on the layer (Y) side in the gas barrier laminate such as the gas barrier film of the present invention.
Examples of the protective layer (U) include epoxy resins, unsaturated polyester resins, phenol resins, urea / melamine resins, polyurethane resins, silicone resins, amino resins, polyimide and other thermosetting resins, polyolefins (polyethylene, polypropylene, poly-4- Methyl 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, Examples include layers made of thermoplastic resins such as ethylene / vinyl acetate copolymer or a saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or a mixture thereof. These protective layers (U) may be laminated directly on the layer (Y), or may be laminated via an adhesive such as an anchor coat.

As another suitable example of the protective layer (U), there is a base material layer (X-1) containing the above-described inorganic fine particles.
By using the base material layer (X-1) containing the inorganic fine particles as a protective layer, a laminate such as a gas barrier film having excellent concealability can be obtained.

As the protective layer (U) containing these inorganic fine particles, any of non-stretched and at least uniaxially stretched layers can be used. The stretched protective layer (U) is excellent in heat resistance, rigidity, transparency and gas barrier properties.
In addition, these protective layers (U) have a surface, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coat treatment, in order to improve adhesion with a gas barrier laminate such as a gas barrier film. Alternatively, surface activation treatment such as frame treatment may be performed.

Examples of gas barrier laminates such as the gas barrier film of the present invention will be described below. However, if the protective layer (U) is abbreviated as (U),
(X) / (Y ¹ ) / (Y ² ) / (U)
(X) / (Y ¹ ) / (Y ² ) / (Y ³ ) / (U)
(X) / (Y ¹ ) / (Z) / (Y ² ) / (U)
(X) / (Z) / (Y ¹ ) / (Y ² ) / (U)
(X) / (Y ¹ ) / (Y ² ) / (Z) / (U)
An example of a laminated structure expressed as “etc.” can be given.
^{Incidentally, (Y 1), (Y} 2), the content of the polymer (a) included in each of ^{(Y 3)} may be the same or may be different from one another. Further, the contents of the polymer (b) contained in each layer may be the same or different.

  In the gas barrier laminate of the present invention, a gas barrier film suitable as a heat-sealable packaging film can be obtained by laminating a heat fusion layer on the surface of the base material layer (X). It is done. As such a heat-fusible layer, a homo- or copolymer of α-olefin such as ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, etc., which are generally known as heat-fusible layers , High pressure method low density polyethylene, linear low density polyethylene (so-called LLDPE), high density polyethylene, polypropylene, polypropylene random copolymer, polybutene, poly-4-methyl pentene-1, low crystalline or amorphous ethylene Polypropylene random copolymer, ethylene / butene-1 random copolymer, polyolefin such as propylene / butene-1 random copolymer, or a composition of two or more, ethylene / vinyl acetate copolymer (EVA), ethylene・ (Meth) acrylic acid copolymer or metal salt thereof, EVA and polyolefin A layer obtained from the object or the like.

Among these, a heat-sealing layer obtained from an ethylene-based polymer such as high-pressure method low-density polyethylene, linear low-density polyethylene (so-called LLDPE), or high-density polyethylene is preferable because it has excellent low-temperature heat sealability and heat seal strength.
Moreover, such a heat sealing | fusion layer is also performed as a protective layer (U) in the outermost layer by the side of the layer (Y) provided in the gas barrier film of this invention as needed.
These heat fusion layers may be laminated via an adhesive or the like, or may be laminated directly.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.

The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
<Evaluation method>
(1) Preparation of multilayer film: 50 μm thick linear low density polyethylene film (trade name: TUX FCS manufactured by Tosero Co., Ltd.) on one side with urethane adhesive (polyurethane adhesive (San Chemical Polyurethane Co., Ltd.) Product name: Takelac A310): 12 parts by weight, isocyanate-based curing agent (product name: Takenate A3, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: 1 part by weight and ethyl acetate: 7 parts by weight) The zinc acrylate polymer layer surface of the gas barrier laminate film obtained in the example was bonded (dry lamination) to obtain a multilayer film.
Further, on one side of a 70 μm-thick unstretched polypropylene film (trade name: RXC-21, manufactured by Tosero), an ester adhesive (polyester adhesive (trade name: Takelac A525, manufactured by Mitsui Chemicals Polyurethane): 9 parts by weight. After applying and drying an isocyanate curing agent (trade name: Takenate A52, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: 1 part by weight and ethyl acetate: 7.5 parts by weight), the gas barrier laminate films obtained in Examples and Comparative Examples The zinc acrylate polymer layer surfaces were bonded together (dry lamination) to obtain a multilayer film.
(2) Retort treatment: The multi-layer film laminated with the non-stretched polypropylene film obtained by the above method is folded so that the non-stretched polypropylene film becomes the inner surface. 40 cc, and the other side was heat sealed to produce a bag (three-side sealed bag), and this was retort-treated at 121 ° C. for 30 minutes with a high-temperature high-pressure retort sterilizer. After the retort treatment, the contents were drained to obtain a multilayer film after the retort treatment.
(3) Oxygen permeability [ml / (m ² · day · MPa)]: The multilayer film obtained by the above method was subjected to a temperature of 20 according to JIS K 7126 using OX-TRAN 2/21 ML manufactured by Mocon. ° C, humidity 90% H. Measure under the following conditions.
(4) Water vapor permeability [g / (m ² · day)]: The multilayer film is folded so that the surface of the linear low-density polyethylene film is on the inside, and after heat-sealing the two sides into a bag shape, the contents Calcium chloride was added, and the other side was heat-sealed to prepare a bag (three-side sealed bag) having a surface area of 0.01 m ² , and this was made into 40 ° C., 90% R.D. H. The water vapor permeability was measured by the difference in weight.

<Preparation of solution (s1)>
A zinc acrylate aqueous solution (manufactured by Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 20 wt%, zinc component 10 wt%)) was diluted to 98.0 wt% in solid content ratio and 25 wt% with methyl alcohol. Photopolymerization initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, manufactured by Ciba Specialty Chemicals) ] In a solid content ratio of 1.3% by weight and a surfactant (trade name: Emulgen 120 manufactured by Kao Corporation) in a solid content ratio of 0.7% by weight, and a zinc acrylate solution (s1) Was made.

<Preparation of solution (s2)>
Mixing aqueous solution of zinc acrylate and acrylate group-modified polyvinyl alcohol Concentration of 14 wt% (zinc acrylate component: 12 wt%, acrylate group-modified polyvinyl alcohol component 2 wt%)] The zinc acrylate component is 88.5 wt% in solid content ratio, the acrylate group-modified polyvinyl alcohol component is 9.7 wt% in solid content ratio, the photopolymerization initiator is 1.2 wt% in solid content ratio, the interface The activator was mixed to a solid content ratio of 0.6% by weight to prepare a solution (s2) composed of zinc acrylate and acrylate group-modified polyvinyl alcohol.

Example 1
The zinc acrylate solution (s1) is applied on the vapor deposition surface of a 12 μm thick aluminum oxide vapor-deposited polyester film (trade name; TL-PET H, manufactured by Tosero Co., Ltd.) using a bar coating method in a solid content of 1. It was coated so as to be 2 g / ^{m 2,} with immediate UV irradiation device coating surface (the eye graphics Co. eYE GRANDAGE model ECS 301G1), illuminance: 180 mW / cm ^2, integrated light quantity: UV at 180 mJ / cm ² conditions And polymerized to form a layer. Furthermore, the mixed solution (s2) of the above zinc acrylate and acrylate group-modified polyvinyl alcohol was applied onto this layer so that the coating amount was 1.2 g / m ² , and the same as when the zinc acrylate solution (s1) was applied. Polymerization was performed by irradiating UV under the conditions described above to provide a layer containing modified polyvinyl alcohol. As a result, a gas barrier laminate film in which two layers of a layer containing no acrylate group-modified polyvinyl alcohol and a layer containing the same was laminated was obtained. Table 1 shows the results of evaluating the obtained laminated film by the method described above.

Example 2
A laminated film was obtained in the same manner as in Example 1 except that the zinc acrylate solution (s1) of the layer not containing the acrylate group-modified polyvinyl alcohol was applied so that the solid content was 0.7 g / m ² . Table 1 shows the results of evaluating the obtained laminated film by the method described above.

Example 3
A laminated film was obtained in the same manner as in Example 1, except that the zinc acrylate solution (s1) of the layer not containing the acrylate group-modified polyvinyl alcohol was applied to a solid content of 0.4 g / m ² . Table 1 shows the results of evaluating the obtained laminated film by the method described above.

Example 4
A laminated film was obtained in the same manner as in Example 3 except that it was applied to the corona-treated surface of a polyester film (trade name; Emblet PET12, manufactured by Unitika Ltd.). Table 1 shows the results of evaluating the obtained laminated film by the method described above.

Comparative Example 1
Example 3 except that the zinc acrylate solution (s1) was applied, the zinc acrylate and acrylate group-modified polyvinyl alcohol mixed solution (s2) was not applied, and only the zinc acrylate polymer layer was formed. Similarly, a laminated film was obtained. The results of evaluating this by the method described above are shown in Table 1.

Comparative Example 2
Example 1 with the exception that the zinc acrylate solution (s1) was not applied, but the mixed solution (s2) of zinc acrylate and acrylate group-modified polyvinyl alcohol was applied to form only a layer containing acrylate group-modified polyvinyl alcohol. Similarly, a laminated film was obtained. The results of evaluating this by the method described above are shown in Table 1.

Comparative Example 3
A laminated film was obtained in the same manner as Comparative Example 2 except that it was applied to the corona-treated surface of a polyester film (trade name; Emblet PET12, manufactured by Unitika Ltd.). The results of evaluating this by the method described above are shown in Table 1.

Comparative Example 4
Table 1 shows the results of evaluating a 12 μm thick aluminum oxide vapor-deposited polyester film (trade name: TL-PET H, manufactured by Tosero Co., Ltd.) by the method described above.

  As apparent from Table 1, a barrier film (Examples 1 to 3) in which a zinc acrylate polymer layer, a zinc acrylate polymer and a layer containing an acrylate group-modified polyvinyl alcohol are adjacently laminated is Compared with the aluminum oxide vapor deposition polyester film (Comparative Example 4) used as the material, the oxygen permeability and water vapor permeability were excellent. Compared with the case of only a polymer layer of zinc acrylate (Comparative Example 1), the oxygen permeability and water vapor permeability are excellent. It can be seen that the barrier property after the retort treatment is very excellent as compared with the case of only the layer containing the polymer of zinc acrylate and the acrylate group-modified polyvinyl alcohol (Comparative Example 2). In addition, when the base material is a polyester film, a barrier film (Example 4) in which a layer containing an acrylate group-modified polyvinyl alcohol and a layer not containing the layer are laminated adjacently is a polymer of zinc acrylate and an acrylate group-modified polyvinyl. It can be seen that the oxygen permeability after the retort treatment is superior to the case of only the layer containing alcohol (Comparative Example 3).

The gas barrier film of the present invention is particularly excellent in gas barrier properties under high humidity by using a plurality of layers (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt. It can be used for various purposes.
Further, when a white film containing inorganic fine particles is used for the protective layer, a gas barrier film having good concealability is obtained.
Taking advantage of these characteristics, the gas barrier film of the present invention is a packaging material for dried foods, water, boiled / retort foods, supplement foods, etc., especially food packaging materials with contents that require particularly high gas barrier properties. First, packaging materials for toiletry products such as shampoos, detergents, baths, and fragrances, pharmaceuticals such as powders, granules, tablets, liquid pharmaceuticals including infusion bags, packaging bags and packaging containers for medical devices, etc. Barrier materials for flat panel displays such as electronic parts packaging materials such as hard disks, wiring boards, and printed boards, liquid crystal displays, plasma displays, inorganic / organic EL displays, electronic paper, and back sheets for solar cells Materials, other electronic materials, vacuum insulation barrier materials, ink cartridges, etc. Such packaging materials, can be suitably used as a protective material for packaging materials for various products or electronic materials, precision components, including pharmaceuticals, hate permeation and moisture of the oxygen gas material.

Claims (5)

  A gas barrier laminate comprising at least two layers (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt in a base material layer.   At least one of the plurality of layers of the layer (Y) containing the polymer (a) is composed of an unsaturated carboxylic acid compound polyvalent metal salt polymer (a) and a vinyl alcohol polymer (b). The gas barrier laminate according to claim 1, wherein   Gas barrier property in which an inorganic vapor deposition layer (Z) is further laminated on the middle of the gas barrier layer in which the base layer (X) and the layer (Y) containing the polymer (a) are laminated or outside the layer (Y). It is a layer, The laminated body of Claim 1 or 2 characterized by the above-mentioned.   Two layers of the plurality of layers (Y) containing the polymer (a) are adjacent to each other, and the proportion of the vinyl alcohol polymer (b) in one layer is the vinyl alcohol type in the other layer. The laminate according to claim 2 or 3, wherein the laminate is lower than a ratio of the polymer.   A laminate comprising a protective layer (U) further laminated on the surface of the gas barrier layer according to any one of claims 1 to 4.